Method of analyzing minute quantity of content

ABSTRACT

A sample preparation for analyzing a minute quantity of a content included in a material is performed by short-time extraction treatment without long-time extraction treatment, and the minute quantity of the content in the material is rapidly analyzed. The method of analyzing a minute quantity of a content includes mounting on a sample table a sample piece of a material to be analyzed; dropping onto the sample table the solvent for extracting the content from the sample piece, and injecting the solvent into a gap between the sample table and the sample piece; maintaining at room temperature the solvent injected into the gap between the sample table and the sample piece, and, with the solvent maintained in the gap between the sample table and the sample piece, extracting the content from the sample piece; and analyzing the content extracted from the sample piece.

TECHNICAL FIELD

The present invention relates to methods of analyzing minute quantitiesof contents in materials, specifically relates to methods of analyzingminute quantities of contents such as additives included in polymermaterials.

BACKGROUND ART

A flowchart is illustrated in FIG. 23 that represents a conventionalmethod of analyzing additives included in polyolefin-group resin such aspolypropylene (referred to as PP) and polyethylene (referred to as PE).First, the additives are extracted for 8 hours with a solvent such aschloroform heated up close to its boiling point, from pellets of thepolyolefin-group resin as a sample (referred to as processing “A”).Here, this extraction is performed twice, and thus, all of the additivesare extracted. Next, after chloroform is removed from the chloroformextract, the reflux extraction is performed for 1 hour using heatedacetone (referred to as processing “B”); then, using this extract afteracetone is removed, analysis is performed by either the liquidchromatography analyzer or the gas chromatography analyzer;consequently, the additives such as an antioxidant and a flame retardantare identified and quantified. On the other hand, regarding the residuesremaining after the chloroform extraction, extraction is performed for 4hours using heated N,N-dimethylformamide (referred to as processing“C”); then, the extract obtained is analyzed by the infrared spectrumanalyzer, and thus, an additive such as a metal deactivator isidentified.

In the processing “A”, an acetone/toluene solvent mixture of 1:1 byvolume ratio can also be used as the solvent other than chloroform. As amethod for the processing “A”, for example, the Soxhlet extractionmethod is used, in which this extraction is not limited to twice, butperformed more than twice in response to necessity. Here, in the Soxhletextraction method used for the processing “A”, because the extraction isperformed with the solution being refluxed, a specified volume of thesolution is needed; thus, as chloroform, for example, the volume ofapproximately 100 ml is needed. Therefore, the amount of approximately10 g is used for the sample pellets. Additionally, in the processing“A”, because the extraction is performed using the solvent heated upclose to its boiling point, due to the resin of the base material beingpartially extracted, this causes interference in the analysis;therefore, by re-extracting the chloroform extract using acetone thatcan only extract the additives, the resin component as the interferencein the analysis is removed. Here, in the processing “A”, if a solventthat extracts only the additives is used, the extraction time becomesfurther long (for example, referred to as Non-Patent Document 1).

[Non-Patent Document 1]

Technical Information Institute, Ed., “Separation and AnalysisTechnology of Polymer Additives”, on page 19-21.

DISCLOSURE OF THE INVENTION

As described above, in the conventional method of analyzing the minutequantity of the content, although the step of analyzing theextract-processed content has not been needed for a long time because ofusing instrumental analysis, regarding the step of preparing the sample,because not only a plural number of extraction treatment using samemethods needed for a long time is performed, but also a plurality ofdifferent methods is also performed, it has been needed for a remarkablylong time consequently, a problem has occurred in which the minutequantity of the content cannot be rapidly identified and quantified.

An objective of the present invention, which is made to solve the abovedescribed problem, is to provide a method of rapidly analyzing a minutequantity of a content included in a material, in which samplepreparation when the minute quantity of the content included in thematerial is analyzed is performed by once short-time extractiontreatment without a plural number of the extraction treatment taking along time and a plurality of different extraction-treatment methods.

According to a first aspect of the present invention, a method ofanalyzing a minute quantity of content by analyzing extract extractedwith a solvent from the content included in a material includes a stepof mounting on a sample table a sample piece of the material to beanalyzed; a step of dropping onto the sample table the solvent forextracting the content from the sample piece, and injecting the solventinto a gap between the sample table and the sample piece; a step ofmaintaining at room temperature the solvent injected into the gapbetween the sample table and the sample piece, and, with the solventmaintained in the gap between the sample table and the sample piece,extracting the content from the sample piece; and a step of analyzingthe content extracted from the sample piece.

According to a second aspect of the present invention, a method ofanalyzing a minute quantity of content by analyzing extract extractedwith a solvent from the content included in a material includes a stepof mounting, in contact with the top face of a sample table, a samplepiece of the material to be analyzed; a step of dropping onto the sampletable the solvent for extracting the content from the sample piece, andinjecting the solvent into a gap between the top face of the sampletable and the sample piece mounted in contact with the top face of thesample table; a step of maintaining at room temperature the solventinjected into the gap between the top face of the sample table and thesample piece, and, with the solvent maintained in the gap between thetop face of the sample table and the sample piece, extracting thecontent from the sample piece; and a step of analyzing the contentextracted from the sample piece.

According to a third aspect of the present invention, in the method ofanalyzing the minute quantity of the content according to the secondaspect, the step of analyzing the content extracted from the samplepiece includes a chromatographic analyzing method of analyzing solutionincluding the content extracted from the sample piece.

According to a forth aspect of the present invention, in the method ofanalyzing the minute quantity of the content according to the secondaspect, the step of analyzing the content extracted from the samplepiece includes a method of, after removing by vaporization of thesolvent in the solution including the content extracted from the samplepiece so as to deposit the content onto the surface of a substrate usedas the sample table, analyzing the content deposited on the surface ofthe substrate.

According to a fifth aspect of the present invention, the method ofanalyzing the minute quantity of the content according to the forthaspect, the method of analyzing the content deposited on the surface ofthe substrate is the time-of-flight secondary ion mass spectrometrymethod.

According to a sixth aspect of the present invention, in the method ofanalyzing the minute quantity of the content according to the secondaspect, as the step of extracting the content from the sample piece, amethod of extracting, by adding vibration in a state in which thesolvent is maintained at room temperature in the gap between the topface of the sample table and the sample piece, using the solventmaintained in the gap between the top face of the sample table and thesample piece, the content from the sample piece is used.

According to a seventh aspect of the present invention, in the method ofanalyzing the minute quantity of the content according to the secondaspect, as the step of extracting the content from the sample piece, amethod of extracting, by maintaining the solvent in the gap between thetop face of the sample table and the sample piece in the saturated vaporatmosphere, at room temperature, of the solvent used for the extraction,using the solvent maintained in the gap between the top face of thesample table and the sample piece, the content from the sample piece isused.

According to an eighth aspect of the present invention, in the method ofanalyzing the minute quantity of the content according to the fifthaspect, the solvent, maintained in the gap between the top face of thesample table and the sample piece, for extracting the content from thesample piece additionally includes a silver composition soluble in thesolvent.

According to the first aspect of the present invention, the method ofanalyzing the minute quantity of the content by analyzing the extractextracted with the solvent from the content included in the materialincludes the step of mounting on the sample table the sample piece ofthe material to be analyzed; the step of dropping onto the sample tablethe solvent for extracting the content from the sample piece, andinjecting the solvent into the gap between the sample table and thesample piece; the step of maintaining at room temperature the solventinjected into the gap between the sample table and the sample piece,and, with the solvent maintained in the gap between the sample table andthe sample piece, extracting the content from the sample piece; and thestep of analyzing the content extracted from the sample piece; thereby,the extraction time can be shortened, and, using a small amount of thesample piece, accurate analysis of the content in the material can beperformed in a short time.

According to the second aspect of the present invention, the method ofanalyzing the minute quantity of the content by analyzing the extractextracted with the solvent from the content included in the materialincludes the step of mounting, in contact with the top face of thesample table, the sample piece of the material to be analyzed; the stepof dropping onto the sample table the solvent for extracting the contentfrom the sample piece, and injecting the solvent into the gap betweenthe top face of the sample table and the sample piece mounted in contactwith the top face of the sample table; the step of maintaining at roomtemperature the solvent injected into the gap between the top face ofthe sample table and the sample piece, and, with the solvent maintainedin the gap between the top face of the sample table and the samplepiece, extracting the content from the sample piece; and the step ofanalyzing the content extracted from the sample piece; thereby, theextraction time can be shortened, and, using a small amount of thesample piece, accurate analysis of the content in polymer material canbe performed in a short time.

According to the third aspect of the present invention, in the method ofanalyzing the minute quantity of the content according to the secondaspect, the step of analyzing the content extracted from the samplepiece includes the chromatographic analyzing method of analyzing thesolution including the content extracted from the sample piece; thereby,the extraction time can be shortened, and, using a small amount of thesample piece, accurate analysis of the content in polymer material canbe performed in a short time.

According to the forth aspect of the present invention, in the method ofanalyzing the minute quantity of the content according to the secondaspect, the step of analyzing the content extracted from the samplepiece includes the method of, after removing by vaporization of thesolvent in the solution including the content extracted from the samplepiece so as to deposit the content onto the surface of the substrateused as the sample table, analyzing the content deposited on the surfaceof the substrate; thereby, the extraction time can be shortened, and,using a small amount of the sample piece, accurate analysis of thecontent in polymer material can be performed in a short time.

According to the fifth aspect of the present invention, the method ofanalyzing the minute quantity of the content according to the forthaspect, the method of analyzing the content deposited on the surface ofthe substrate is the time-of-flight secondary ion mass spectrometrymethod; thereby, the extraction time can be shortened, and, using asmall amount of the sample piece, accurate analysis of the content inpolymer material can be performed in a short time. Especially, analysisof the minute quantity of the content becomes possible.

According to the sixth aspect of the present invention, in the method ofanalyzing the minute quantity of the content according to the secondaspect, as the step of extracting the content from the sample piece, themethod of extracting, by adding vibration in the state in which thesolvent is maintained at room temperature in the gap between the topface of the sample table and the sample piece, using the solventmaintained in the gap between the top face of the sample table and thesample piece, the content from the sample piece is used; thereby, theextraction time can be shortened, and, using a small amount of thesample piece, accurate analysis of the content in polymer material canbe performed in a short time. Especially, because the amount of theextract from the sample piece increases, the analysis accuracy of theextract improves.

According to the seventh aspect of the present invention, in the methodof analyzing the minute quantity of the content according to the secondaspect, as the step of extracting the content from the sample piece, themethod of extracting, by maintaining the solvent in the gap between thetop face of the sample table and the sample piece in the saturated vaporatmosphere, at room temperature, of the solvent used for the extraction,using the solvent maintained in the gap between the top face of thesample table and the sample piece, the content from the sample piece isused; thereby, the extraction time can be shortened, and, using a smallamount of the sample piece, accurate analysis of the content in polymermaterial can be performed in a short time. Especially, because there-dropping of the solvent used for the extraction becomes unnecessary,the analysis process becomes simple.

According to the eighth aspect of the present invention, in the methodof analyzing the minute quantity of the content according to the fifthaspect, the solvent, maintained in the gap between the top face of thesample table and the sample piece, for extracting the content from thesample piece additionally includes the silver composition soluble in thesolvent; thereby, the extraction time can be shortened, and, using asmall amount of the sample piece, accurate analysis of the content inpolymer material can be performed in a short time. Especially, thesensitivity; using the time-of-flight secondary ion mass spectrometrymethod, for analyzing the extract from the material is remarkablyimproved.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a flow chart explaining a method of analyzing a minutequantity of a content included in a material according to the presentinvention;

FIG. 2 is views illustrating states in which an extraction solvent isdropped, according to the analyzing method of the present invention;

FIG. 3 is a view illustrating a state, according to the analyzing methodof the present invention, in which a sample piece is mounted in contactwith the top face of a sample table, and the extraction solvent ismaintained in gaps between the top face of the sample table and thesample piece;

FIG. 4 is views representing a first method, of preparing a specimen,for analyzing extract by an analyzer, according to an analyzing methodof the present invention;

FIG. 5 is views illustrating a second method, of preparing a specimen,for analyzing extract by an analyzer, according to an analyzing methodof the present invention;

FIG. 6 is, as an example of the measurement results according to Example1, a chromatogram of extraction solution extracted from an HDPE pelletincluding an antioxidant of 500 ppm;

FIG. 7 is a graph representing a relationship between areas of the peaks“A” obtained from the chromatograms in which the extraction solutionsextracted from the HDPE pellets each including the antioxidant of 50ppm, 100 ppm, 500 ppm, or 1000 ppm as the concentration, and theantioxidant concentrations, according to Example 1;

FIG. 8 is, as an example of the measurement results according to Example2, an infrared absorption spectrum of extract extracted from a PP pelletincluding a brominated flame retardant of 0.1%;

FIG. 9 is a graph representing a relationship between the absorbancevalues of the infrared absorption peaks obtained from the analysis inwhich the extracts are extracted from the PP pellets each including thebrominated flame retardant of 0.1%, 1%, or 10% as the concentration, andthe brominated flame-retardant concentrations, according to Example 2;

FIG. 10 is, as an example of the measurement results according toExample 3, a photoelectron spectrum of extract extracted from the PPpellet including the brominated flame retardant of 0.1%;

FIG. 11 is a graph representing a relationship between the peak areas atclose to 69 eV of the photoelectron spectra obtained from the analysisin which the extracts are extracted from the PP pellets each includingthe brominated flame retardant of 0.1%, 1%, or 10% as the concentration,and the brominated flame-retardant concentrations, according to Example3;

FIG. 12 is, as an example of the measurement results according toExample 4, a mass spectrum of extract extracted from the HDPE pelletincluding the antioxidant of 500 ppm;

FIG. 13 is a graph representing a relationship between the mass-spectrumpeak-area ratios (⁷⁷⁵M⁺/²⁸Si⁺) obtained from the analysis in which theextracts are extracted from the HDPE pellets each including theantioxidant of 10 ppm, 50 ppm, 100 ppm, 500 ppm, or 1000 ppm as theconcentration, and the antioxidant concentrations, according to Example4;

FIG. 14 is, as an example of the measurement results according toExample 5, a mass spectrum of extract extracted from a PP pelletincluding the brominated flame retardant of 100 ppm;

FIG. 15 is a graph representing a relationship between the mass-spectrumpeak-area ratios (⁷⁹Br⁻/¹⁰⁷Ag⁻) obtained from the analysis in which theextracts are extracted from the PP pellets each including the brominatedflame retardant of 1 ppm, 10 ppm, 100 ppm, 1000 ppm, 1%, or 10% as theconcentration, and the brominated flame retardant concentrations,according to Example 5;

FIG. 16 is, as an example of the measurement results according toExample 6, a mass spectrum of extract extracted from an HIPS pelletincluding the brominated flame retardant of 0.1%;

FIG. 17 is a graph representing a relationship between the mass-spectrumpeak-area ratios (¹⁰⁶⁸(B+Ag)⁺/¹⁰⁷Ag⁺) obtained from the analysis inwhich the extracts are extracted from the HIPS pellets each includingthe brominated flame retardant of 0.1%, 1%, or 10% as the concentration,and the brominated flame retardant concentrations, according to Example6;

FIG. 18 is a view representing a state in which content is extractedfrom a sample piece according to Example 7;

FIG. 19 is a mass spectrum of the extract, obtained by the methodaccording to Example 7, extracted from the HDPE pellet including theantioxidant of 500 ppm;

FIG. 20 is a view representing a state according to Example 8, in whicha content is extracted from a sample piece;

FIG. 21 is a mass spectrum of the extract, obtained by the methodaccording to Example 8, extracted from the PP pellet including thebrominated flame retardant of 100 ppm;

FIG. 22 is a mass spectrum of extract, obtained by a method according toExample 9, extracted from the HIPS pellet including the brominated flameretardant of 0.1%; and

FIG. 23 is a flowchart representing a conventional method of analyzingan additive included in polyolefin-group resin.

BEST MODE FOR CARRYING OUT THE INVENTION

FIG. 1 is a flow chart explaining a method of analyzing a minutequantity of a content included in a material according to the presentinvention. In a first step, a sample piece 1 of the material including asubstance to be analyzed is mounted in contact with the top face of asample table 2 (FIG. 1( a)). In a second step, a solvent 3 forextracting the content from the sample piece 1 is dropped onto the topface of the sample table 2 so as to inject the solvent into the gapsbetween the top face of the sample table 2 and the sample piece 1(hereinafter referred to as “gaps between the sample table 2 and thesample piece 1”) (FIG. 1( b)). In a third step, the solvent 3 injectedinto the gaps between the sample table 2 and the sample piece 1 is keptfor a short time at room temperature; thus, by the solvent 3 maintainedin the gaps between the sample table 2 and the sample piece 1, thecontent to be analyzed is extracted from the sample piece 1 (FIG. 1(c)). In a forth step, the content extracted from the sample piece 1 isanalyzed by an instrumental analyzer 10 (FIG. 1( d)).

In the analyzing method according to the present invention, as thematerial to be analyzed, polymer materials such as plastic, rubber,adhesives, encapsulating resin, and mold resin are listed. These polymermaterials are analyzed not only in the state of the materialsthemselves, but also in a state in which the materials are used ininstrumental parts such as an instrumental case, a molded product, and aprinted wiring board. In the analyzing method according to the presentinvention, as materials to be analyzed, a sub-material such as anantioxidant, a fire retardant, a curing catalyst, or a processing aidincluded in a polymer material, as well as a minute quantity of asubstance that may be included either during the material itself beingproduced, or during the material being molded/processed into variousparts of a product can be listed; however, if the substance that can beextracted with a solvent from the polymer material to be applied isused, the material is not limited to the above. In the analyzing methodaccording to the present invention, a little amount of the sample piecesuch as an approximately one resin-pellet amount (for example, 0.1-0.5 gin weight) may also be used.

In the analyzing method according to the present invention, as thesample table for mounting the sample piece, any table having a flat facethat can mount the sample piece may be applied, and especially, asubstrate is preferably applied. As the materials of the sample table, aglass material, an inorganic material, a metallic material, and aplastic material having chemical resistance, etc. that do not includethe substance to be analyzed, are listed. When the liquid chromatographymethod, the gas chromatography method, or theliquid-chromatography/mass-spectrometry method is applied as theanalyzing method, specifically, for example, a glass substrate, asilicon substrate, a germanium substrate, a silver substrate, a goldsubstrate, a poly(tetrafluoroethylene) substrate, an SUS substrate onwhich poly(tetrafluoroethylene) is coated, a glass Petri dish, a silvercontainer, a gold container, or a poly(tetrafluoroethylene) container isused as the table. When the infrared spectrum analysis is applied as theanalyzing method, specifically, for example, a silicon substrate, agermanium substrate, or an SUS substrate on whichpoly(tetrafluoroethylene) is coated is used. Moreover, when the X-rayphotoelectron spectroscopy method is applied as the analyzing method, asilicon substrate is used. Furthermore, when the time-of-flightsecondary ion mass spectrometry method is applied as the analyzingmethod, for example, a silicon substrate, a germanium substrate, asilver substrate, a gold substrate, or an SUS substrate on which silveror gold is plated is used.

FIG. 2 is views illustrating states in which the extraction solvent isdropped, according to the analyzing method of the present invention. Asrepresented in FIG. 2, the extraction solvent 3 is dropped using amicrosyringe 4 onto the top face of the sample table 2 with which thepellet of the sample piece 1 is mounted in contact. In FIG. 2, asubstrate as the sample tables 2 is represented as an example;hereinafter, a substrate 2 is explained as the sample table 2. However,according to the present invention, the sample table 2 is not limited tothe substrate. Regarding the dropping volume of the extraction solvent3, the volume may be from a volume that can at least fill the gapsbetween the substrate 2 and the sample piece 1 to a volume that is twicethe volume of the sample piece; thereby, for example, when the samplepiece 1 is a single resin-pellet, the volume is 5-100 μl. Moreover, ifthe position to be dropped is on the top face of the substrate 2, theposition is not especially limited; however, it is preferable to dropthe solvent at a position, on the top face of the substrate 2, close toa portion on which the sample piece 1 is mounted, specifically, to dropat the boundary between the portion on which the sample piece 1 ismounted and the portion on which the sample piece 1 is not mounted,because the solvent 3 can be effectively injected into the gaps betweenthe substrate 2 and the sample piece 1.

FIG. 3 is a view illustrating a state in which the sample piece 1 ismounted in contact with the top face of the substrate as the sampletable 2. As represented in FIG. 3, the sample piece 1 has recesses andprotrusions on its face contacting to the substrate 2; thereby, theseprotrusions contact to the top face of the substrate 2, meanwhile theserecesses form gaps 9 between the substrate 2 and the sample piece 2, andthus, the solvent dropped is injected into the gaps 9. In the extractionof the content from the sample piece 1 according to the analyzing methodof the present invention, the state in which the solvent 3 is at leastmaintained in the gaps 9 between the substrate 2 and the sample piece 1is held at room temperature for a short time; thereby, the content isextracted into the solvent 3 contacting to the sample piece, especiallyinto the solvent 3 existing in the gaps between the substrate 2 and thesample piece 1. At this time, because the solvent decreases due to itsvaporization, after a predetermined time passes, the solvent 3 may bedropped again. For example, if the sample piece 1 is the singleresin-pellet, the extraction time, that is, the time during the state inwhich the solvent 3 is maintained in the gaps between the substrate 2and the sample piece 1 being held, and the content being extracted ispreferably set for 0.5-30 minutes, and further preferably set for 0.5-15minutes. If this time is shorter than 0.5 minutes, the extractionbecomes insufficient; thereby, the analysis accuracy deteriorates. Onthe other hand, if the time is longer than 30 minutes, the repeatingnumber of the dropping only increases without increase of the extractamount; thereby, not only the analysis process becomes more complex, butalso the analysis time becomes longer.

Moreover, in order to increase the amount of the content extracted fromthe sample piece 1 into the solvent 3, the substrate 2 may be vibratedduring the extraction. As the vibration method, a method of using anultrasonic washer or a shaker, and a method in which an ultrasonicoscillator is pasted onto the substrate 2 are listed. Furthermore, byputting into a sealed container the substrate 2, the sample piece 1, andthe solvent 3 maintained in the gaps between the substrate 2 and thesample piece 1, the extraction of the content may be performed from thesample piece 1 using the extraction solvent 3, in the saturated vaporatmosphere of the same solvent as the extraction solvent 3. According tothis operation, loss of the extraction solvent 3 due to the vaporizationis prevented, and additional dropping of the solvent becomes needless;consequently, the analyzing process can be simplified.

FIG. 4 is views representing a first method, of preparing a specimen,for analyzing the extract by an analyzer, according to an analyzingmethod of the present invention. This first method is especially usedwhen the extract is analyzed by a chromatographic analyzing method suchas the liquid chromatography method, the gas chromatography method, orthe liquid-chromatography/mass-spectrometry method. As represented inFIG. 4, after the extraction step has finished, the test piece 1 isremoved from the substrate 2; then, solution 5 including the extractplaced on the top face of the substrate 2 is sampled using amicrosyringe 6 into a sample cell 7. Then, this sampled solution 5 isinjected into the analyzer, and the content included in the polymermaterial is analyzed.

FIG. 5 is views illustrating a second method, of preparing a specimen,for analyzing the extract by an analyzer, according to an analyzingmethod of the present invention. This second method is used when theextract is analyzed by any one of the X-ray fluorescence spectrometrymethod, the time-of-flight secondary ion mass spectrometry method, theinfrared spectrometry method, and the X-ray photoelectron spectroscopymethod. As represented in FIG. 5, after the extraction step hasfinished, the test piece 1 is removed from the substrate 2, and then,the solvent of the solution 5 including the extract placed on the topface of the substrate 2 is removed by vaporization; thus, the substratesurface on which extract 8 is deposited is directly analyzed by theanalyzer. In the analyzing method of the present invention, especially,when the extract is analyzed using the time-of-flight secondary ion massspectrometry method, because if the extract exists too much, thedeposition portion is charged up; therefore, in order to prevent thecharging up, it is preferable that a silver substrate, a gold substrate,or an SUS substrate on which silver or gold is plated is used as thesubstrate. In the analyzing method of the present invention, as thesolvent used for extracting, a solvent is used that extracts the contentwithout decomposing the polymer material at room temperature. Regardingthe grade of the solvent used, a solvent having the analysis gradepurity is preferably used because of little influence on analyzing thecontent.

In the analyzing method of the present invention, especially, when theextract is analyzed using the time-of-flight secondary ion massspectrometry method, the content is resolved in a solvent forextraction, and, if the solution is used in which a silver compound thatdoes not include as an impurity the substance to be measured is added,not only the charging up can be prevented even if a chargeable substrateis used, but also the analysis sensitivity is improved; consequently,the analysis accuracy is improved. In the analyzing method of thepresent invention, the sample piece is mounted in contact with the topface of the sample table such as the substrate, the solvent is injectedby dropping into the gaps between the sample table and the sample piece,the solvent injected is maintained in the gaps between the sample tableand the sample piece, the content is extracted with this maintainedsolvent, and the extract is analyzed by the analyzer; therefore, theextraction time can be shortened, and using a small amount of the samplepiece, accurate analysis of the content in the material, especially inthe polymer material, can be performed in a short time. Hereinafter,more specific examples according to the present invention arerepresented; however, the present invention is not limited to theseexamples.

EXAMPLES Example 1

High density polyethylene (hereinafter referred to as HDPE) specimenseach including an antioxidant of 50 ppm, 100 ppm, or 1000 ppm by weightwere prepared. HJ340™ (produced by Japan Polychem Corp.) was used asHDPE, and 1,3,5-trimethyl-2,4,6tris(3,5-di-tert-buthyl-4-hydroxybenzyl)benzene (Irganox 1330™, producedby Aldrich Corp.) was used as the antioxidant. As the sample piece 1,the antioxidant was added to and kneaded with the HDPE so that theconcentration becomes above each value; thus, pellets were prepared inwhich the size of the single pellet is 5 mm×3 mm×3 mm, and the weight isapproximately 0.2 g. Similarly to the method represented in FIG. 2, thesingle HDPE pellet as the sample piece 1 was mounted in contact with asilicon substrate as the sample table 2, and 20 μl chloroform as theextraction solvent 3 was dropped using the microcyringe 4 so that thechloroform is injected into the gaps between the HDPE pellet and thesilicon substrate; then, the sample piece was kept. Chloroform is asolvent that does not dissolve the HDPE, but dissolves the aboveantioxidant. The sample was kept at room temperature for 10 minutesafter the dropping operation; however, because the volume of thechloroform decreases during the maintaining due to the vaporization, 20μl chloroform was additionally dropped for every two minutes. Thechloroform used was the liquid chromatography grade one (produced byWako Pure Chemical Industries, Ltd.).

Similarly to the method represented in FIG. 4, after the sample was keptfor 10 minutes, the HDPE pellet as the sample piece 1 was removed fromthe silicon substrate as the sample table 2. Next, the chloroformsolution as the solution 5 including extract remaining on the top faceof the silicon substrate was transferred into the sample cell 7 usingthe microcyringe 6, and then, adjusted to a constant volume of 50 μl.The time required from the start to now was 12 minutes. The solution inthis sample cell 7 was injected into theliquid-chromatography/mass-spectrometry analyzer, and thus, the amountof the antioxidant was measured. Model HP8900™ (manufactured by AgilentTechnologies Inc.) was used as the liquid chromatography, Model LC-mate™(manufactured by JEOL Ltd.) was used as the mass spectrometry, andInertsil ODS-3™ (manufactured by GL Sciences Inc.) having the columninner diameter of 4.6 mm and the length of 150 mm was used as a columnfor separating organic compounds. Regarding the measurement condition ofthe liquid chromatography, the gradient mode using methanol and water asthe eluent was applied, and the flow rate was set at 1 ml/minute.Regarding the measurement condition of the mass spectrometry, theatmospheric pressure chemical ionization method was used as anionization method, the positive-ion mode was used, and themass-to-charge ratio (referred to as “m/z”) that is the ratio of thefragment mass number “m” to the charge “z” was set to 1-1000 as themeasurement range; thus, the scanning measurement was performed.

FIG. 6 is, as an example of the measurement results, a chromatogram ofthe extraction solution extracted from the HDPE pellet including theantioxidant of 500 ppm. The peak “A” represents the separated peak ofthe antioxidant, while the peak “B” represents a silane coupling agentincluded in the pellet. Identification of these peaks was confirmed bychecking the mass spectrum and the retention times of the chromatogrambased on the measurement of the standard sample using correspondingsubstances. The peak area of the peak “A” was 5000 counts. FIG. 7 is agraph representing a relationship between areas of the peaks “A”obtained from the chromatograms in which the extraction solutionsextracted from the HDPE pellets each including the antioxidant of 50ppm, 100 ppm, 500 ppm, or 1000 ppm as the concentration, and theantioxidant concentrations. An excellent linear relationship wasobtained between the antioxidant concentrations and the areas of thepeaks “A” obtained from the chromatograms. In this example, theprocessing time was 12 minutes for extracting the antioxidant as thecontent from the HDPE pellet; thereby, it was found that thequantitative analysis of the antioxidant as the content can be performedby short-time extraction treatment. As described above, in the analyzingmethod according to this example, the extraction processing time can beconsiderably shortened compared to that in the conventional method, andthe antioxidant as the content included in the HDPE specimen can berapidly analyzed.

Example 2

PP specimens each including as an additive a brominated flame retardantof 0.1%, 1%, or 10% by weight were prepared as samples. PC03B™ (producedby Japan Polychem Corp.) was used as PP, and decabromodiphenylether(produced by Wako Pure Chemical Industries, Ltd.) was used as thebrominated flame retardant. As the sample piece 1, the brominated flameretardant was added to and kneaded with the PP so that the concentrationbecomes above each value; thus, pellets were prepared in which the sizeof the single pellet is 5 mm×3 mm×3 mm, and the weight is approximately0.2 g. Similarly to the method represented in FIG. 2, the single PPpellet as the sample piece 1 was mounted in contact with an SUSsubstrate coated with fluororesin as the sample table 2, and 20 μltoluene as the extraction solvent 3 was dropped using the microcyringe 4so that the toluene is injected into the gaps between the PP pellet andthe SUS substrate coated with fluororesin; then, the sample piece waskept. Toluene is a solvent that does not dissolve PP, but dissolves theabove brominated flame retardant. The sample was kept at roomtemperature for 10 minutes after the dropping operation; however,because the volume of the toluene decreases during the maintaining dueto the vaporization, 20 μl toluene was additionally dropped after fiveminutes. The toluene used was the liquid chromatography grade one(produced by Wako Pure Chemical Industries, Ltd.). Because after 10minutes from the first toluene drop, the dropped toluene had beenremoved by vaporization, the PP pellet and the substrate were in a drystate. Then, when the PP pellet was removed from the substrate,similarly to the case represented in FIG. 5, extract from the pellet wasdeposited on the surface of the substrate as a condensed substance.

This deposited substance on the surface of the substrate was analyzed bythe microscopic Fourier-transform infrared spectroscopic method. ModelJIR-5500™ (manufactured by JEOL Ltd.) was used as the microscopicFourier-transform infrared spectrometer. Regarding the measurementcondition, the reflection mode was used, in which the measurementwavenumber range was set to 700-4000 cm⁻¹, and the wavenumber resolutionwas set at 2 cm⁻¹. FIG. 8 is, as an example of the measurement results,an infrared absorption spectrum of the extract extracted from the PPpellet including the brominated flame retardant of 0.1%. As representedin FIG. 8, the infrared absorption peak caused by decabromodiphenyletherwas observed close to 1300 cm⁻¹. FIG. 9 is a graph representing arelationship between the absorbance values of the infrared absorptionpeaks obtained from the analysis in which the extract is extracted fromthe PP pellets each including the brominated flame retardant of 0.1%,1%, or 10% as the concentration, and the brominated flame-retardantconcentrations. An excellent linear relationship was obtained betweenthe brominated flame-retardant concentrations and the absorbance valuesof the infrared absorption peaks. In this example, the processing timewas 10 minutes for extracting the brominated flame retardant as thecontent from the PP pellet; thereby, it was found that the quantitativeanalysis of the brominated flame retardant as the content can beperformed by short-time extraction treatment. As described above, in theanalyzing method according to this example, the extraction processingtime can be considerably shortened compared to that in the conventionalmethod, and the brominated flame retardant as the content included inthe PP specimen can be rapidly analyzed.

Example 3

Except for a silicon substrate being used as the substrate to be thesample table 2, similarly to the procedure in Example 2, the dropoperation using the extraction solvent, the extraction operation, andthe deposition/fixation operation of the extract were performed. In thisexample, the deposited substance on the surface of the substrate wasanalyzed by the X-ray photoelectron spectroscopy method. ModelQUANTUM2000™ (manufactured by Physical Electronics Industries Inc.) wasused as the X-ray photoelectron spectroscopic analyzer, and themeasurement range was set to 60-80 eV. FIG. 10 is, as an example of themeasurement results, a photoelectron spectrum of the extract extractedfrom the PP pellet including the brominated flame retardant of 0.1%. Asrepresented in FIG. 10, the photoelectron spectrum caused by the3d_(3/2) and 3d_(5/2) orbits of bromine included indecabromothphenylether was observed close to 69 eV, and the spectrumpeak area was 20. FIG. 11 is a graph representing a relationship betweenthe peak areas at 69 eV of the photoelectron spectra obtained from theanalysis in which the extract is extracted from the PP pellets eachincluding the brominated flame retardant of 0.1%, 1%, or 10% as theconcentration, and the brominated flame-retardant concentrations. Anexcellent linear relationship was obtained between the brominatedflame-retardant concentrations and the peak area. In this example, theprocessing time was 10 minutes for extracting the brominated flameretardant as the content from the PP pellet; thereby, it was also foundthat the quantitative analysis of the brominated flame retardant as thecontent can be performed by a short-time extraction operation. Asdescribed above, in the analyzing method according to this example, theextraction processing time can also be considerably shortened comparedto that in the conventional method, and the brominated flame retardantas the content included in the PP specimen can be rapidly analyzed.

Example 4

Except for HDPE pellets each including the antioxidant of 10 ppm, 50ppm, 100 ppm, 500 ppm, or 1000 ppm by weight being prepared as thesample pieces 1, similarly to the procedure in Example 1, the dropoperation using the extraction solvent, and the extraction operationwere performed. In this example, after ten minutes passed from the firstdropping of chloroform, the HDPE pellet was removed from the top face ofthe substrate without dropping chloroform again. Next, the substrate waskept for two minutes at room temperature so that the chloroform isremoved by vaporization; thus, extract from the pellet was deposited asa condensed substance on the surface of the substrate. In this example,the deposited substance on the surface of the substrate was analyzed bythe time-of-flight secondary ion mass spectrometry method. TRIFT2™(manufactured by ULVAC-PHI Inc.) was used as the time-of-flightsecondary ion mass spectrometry analyzer. Regarding the measurementcondition, ⁶⁹Ga⁺ ion was used as the primary ion, the measurement modeof the secondary ion was set to the positive ion mode, the measurementrange was set to m/z=1-1000, and the mass resolution was set toapproximately ΔM/M=5000.

FIG. 12 is, as an example of the measurement results, a mass spectrum ofthe extract extracted from the HDPE pellet including the antioxidant of500 ppm. As represented in FIG. 12, the mass peak caused by the fragmentof the antioxidant was observed at m/z=775. Quantitative analysis wasperformed using the normalized (⁷⁷⁵M⁺/²⁸Si⁺) area ratio in which thearea of the peak at m/z=775 (⁷⁷⁵M⁺) is normalized by the area of thepeak at m/z=28 (²⁸Si⁺) caused by the fragment of silicon included in thesubstrate. The area ratio of the extract extracted from the HDPE pelletincluding the antioxidant of 500 ppm was 5. FIG. 13 is a graphrepresenting a relationship between the mass-spectrum peak-area ratios(⁷⁷⁵M⁺/²⁸Si⁺) obtained from the analysis of the extracts extracted fromthe HDPE pellets each including the antioxidant of 10 ppm, 50 ppm, 100ppm, 500 ppm, or 1000 ppm as the concentration, and the antioxidantconcentrations. An excellent linear relationship was obtained betweenthe antioxidant concentrations and the peak-area ratios (⁷⁷⁵M⁺/²⁸Si⁺),and especially, it was found to be also detectable at the minuteconcentration of 10 ppm. In this example, the processing time was 12minutes for extracting the antioxidant as the content from the HDPEpellet; thereby, it was found that the quantitative analysis, also up tosuch minute concentration, of the antioxidant as the content can beperformed by a short-time extraction operation. As described above, inthe analyzing method according to this example, the extractionprocessing time can also be considerably shortened compared to that inthe conventional method, and the antioxidant minutely included, forexample, 10 ppm, in the HDPE specimen can be rapidly analyzed.

Example 5

Similarly to the method in Example 2, PP pellets each including thebrominated flame retardant of 1 ppm, 10 ppm, 100 ppm, 1000 ppm, 1%, or10% by weight concentration were prepared as the sample pieces 1. Next,except for a silver substrate being used for a substrate as the sampletable 2, similarly to the procedure in Example 2, extract from each PPpellet was deposited as a condensed substance on the surface of thesubstrate. In this example, the deposited substance on the surface ofthe substrate was analyzed by the time-of-flight secondary ion massspectrometry method. TRIFT2™ (manufactured by ULVAC-PHI Inc.) was usedas the time-of-flight secondary ion mass spectrometry analyzer.Regarding the measurement condition, ⁶⁹Ga⁺ ion was used as the primaryion, the measurement mode of the secondary ion was set to the negativeion mode, the measurement range was set to m/z=1-200, and the massresolution was set to approximately ΔM/M=5000. FIG. 14 is, as an exampleof the measurement results, a mass spectrum of the extract extractedfrom the PP pellet including the brominated flame retardant of 100 ppm.As represented in FIG. 14, the mass-spectrum peak caused by the fragmentof the bromine element was observed at m/z=79. Quantitative analysis wasperformed using the normalized (⁷⁹Br⁻/¹⁰⁷Ag⁻) peak-area ratio in whichthe area of the peak at m/z=79 (⁷⁹Br⁻) is normalized by the area of thepeak at m/z=107 (¹⁰⁷Ag⁻) caused by the fragment of silver in thesubstrate.

FIG. 15 is a graph representing a relationship between the mass-spectrumpeak-area ratios (⁷⁹Br⁻/¹⁰⁷Ag⁻) obtained from the analysis of theextracts extracted from the PP pellets each including the brominatedflame retardant of 1 ppm, 10 ppm, 100 ppm, 1000 ppm, 1%, or 10% as theconcentration, and the brominated flame retardant concentrations. Anexcellent linear relationship was obtained between the brominated flameretardant concentrations and the peak-area ratios, and especially, itwas found to be also detectable at the minute concentration of 1 ppm. Inthis example, the processing time was 10 minutes for extracting thebrominated flame retardant as the content from the PP pellet of thesample piece 1; thereby, it was found that the quantitative analysis,also up to such minute concentration, of the brominated flame retardantas the content can be performed by a short-time extraction operation. Asdescribed above, in the analyzing method according to this example, theextraction processing time can also be considerably shortened comparedto that in the conventional method, and the brominated flame retardantminutely included, for example, 1 ppm, in the PP specimen can be rapidlyanalyzed.

Example 6

High impact polystyrene (referred to as HIPS) specimens each includingbrominated flame retardant as the additive of 0.1%, 1%, or 10% by weightwere prepared as the samples. H8672™ (produced by PS Japan Corp.) wasused as the HIPS, and decabromodiphenylether (produced by Wako PureChemical Industries, Ltd.) was used as the brominated flame retardant.As the sample piece 1, the brominated flame retardant was added to andkneaded with the HIPS so that the concentration becomes above eachvalue; thus, pellets were prepared in which the size of the singlepellet is 5 mm×3 mm×3 mm, and the weight is approximately 0.3 g.Similarly to the procedure represented in FIG. 2, the single HIPS pelletas the sample piece 1 was mounted in contact with a silver substrate asthe sample table 2, a mixed solvent of toluene and methanol(toluene/methanol=1/1 by volume) as the extraction solvent 3 of 20 μlwas dropped, using the microcyringe 4, close to the HIPS pellet, so asto inject the mixed solvent into the gaps between the HIPS pellet andthe silver substrate, and then, the sample piece was kept. This mixedsolvent is a solvent for extracting not only the HIPS but also thebrominated flame retardant. Then, after 30 seconds passed from the dropoperation, the HIPS pellet was removed from the silver substrate,nitrogen gas was blown onto the surface of the silver substrate on whichthe HIPS pellet was removed, and the solvent containing the brominatedflame retardant was dried; thus, extract was deposited on the surface ofthe silver substrate. The processing time was approximately one minutefrom this mixed solvent being dropped until the extract was depositedonto the surface of the silver substrate. The grades of toluene andmethanol used in this example were the liquid chromatographic ones(produced by Wako Pure Chemical Industries, Ltd.).

In this example, the deposited substance on the surface of the substratewas analyzed by the time-of-flight secondary ion mass spectrometrymethod. TRIFT2™ (manufactured by ULVAC-PHI Inc.) was used as thetime-of-flight secondary ion mass spectrometry analyzer. Regarding themeasurement condition, ⁶⁹Ga⁺ ion was used as the primary ion, themeasurement mode of the secondary ion was set to the positive ion mode,the measurement range was set to m/z=1-1500, and the mass resolution wasset to approximately ΔM/M=5000. FIG. 16 is, as an example of themeasurement results, a mass spectrum of the extract extracted from theHIPS pellet including the brominated flame retardant of 0.1%. Asrepresented in FIG. 16, the mass-spectrum peak caused by the peak B⁺ dueto the fragment of decabromodiphenylether as the brominated flameretardant and the peak Ag⁺ due to the fragment of silver was observed atm/z=1068. Quantitative analysis was performed using the normalized(¹⁰⁶⁸(B+Ag)⁺/¹⁰⁷Ag⁺) peak-area ratio in which the area of the peak atm/z=1068 (¹⁰⁶⁸(B+Ag)⁺) is normalized by the area of the peak at m/z=107(¹⁰⁷Ag⁺). The above area ratio of the extract extracted from the HIPSpellet including the brominated flame retardant of 0.1% was 0.005.

FIG. 17 is a graph representing a relationship between the mass-spectrumpeak-area ratios (¹⁰⁶⁸(B+Ag)⁺/¹⁰⁷Ag)⁺) obtained from the analysis of theextracts being extracted from the HIPS pellets each including thebrominated flame retardant of 0.1%, 1%, or 10% as the concentration, andthe brominated flame retardant concentrations. An excellent linearrelationship was obtained between the brominated flame retardantconcentrations and the peak-area ratios. In this example, the processingtime was 1 minute for extracting the brominated flame retardant as thecontent from the HIPS pellet; thus, it was determined that thequantitative analysis, up to also the minute concentration, of thebrominated flame retardant as the content can be performed by anextremely short-time extraction operation. As described above, in theanalyzing method according to this example, the extraction processingtime can be considerably shortened compared to that in the conventionalmethod, and a content included in a matrix that is soluble in a solventextracting the content, such as the brominated flame retardant includedin the HIPS specimen, can also be rapidly analyzed.

Example 7

In this example, similarly to the method in Example 4, an HDPE pelletincluding the antioxidant of 500 ppm by weight was prepared. This HDPEpellet as the sample piece 1 was mounted in contact with a siliconsubstrate as the sample table 2; then, similarly to the method inExample 4, after chloroform as the extraction solvent 3 was dropped andinjected into the gaps between the HDPE pellet and the siliconsubstrate, the sample piece was kept. Then, by processing for 12 minutessimilarly to the procedure in Example 4, the antioxidant was extractedinto the solvent, and this antioxidant as the extract was deposited as acondensed substance onto the surface of the substrate. FIG. 18 is a viewrepresenting a state in which the content is extracted from the samplepiece according to this example. As represented in FIG. 18, a support 43is placed inside a washing bath 42, into which ion exchanged water isput, of an ultrasonic washer 41, and a silicon substrate 12 is mountedon the support 43. An HDPE pellet 11 is mounted in contact with the topface of this silicon substrate 12, and chloroform 13 is maintained inthe gaps between the top face of the silicon substrate 12 and the HDPEpellet 11. Thus, in this example, during extraction processing,ultrasonic vibration, for example, at a frequency of 45 kHz, is added tothe HDPE pellet 11, the chloroform 13, and the silicon substrate 12. Theultrasonic washer used in this example is Branson-Series Type 2510J-DTA™(manufactured by Yamato Scientific Co., Ltd.).

Similarly to the method in Example 4, the deposited substance wasanalyzed by the time-of-flight secondary ion mass spectrometry method.FIG. 19 is a mass spectrum of the extract, obtained by the methodaccording to this example, extracted from the HDPE pellet including theantioxidant of 500 ppm. As represented in FIG. 19, the mass peak due tothe fragment of the antioxidant was observed at m/z=775. The normalized(⁷⁷⁵M⁺/²⁸Si⁺) area ratio in which the area of the peak at m/z=775(⁷⁷⁵M⁺) is normalized by the area of the peak at m/z=28 (²⁸Si⁺) causedby the fragment of silicon in the substrate was 25, which is five timeslarger than that of Example 4 in which the ultrasonic waves were notadded during the extraction operation. That is, by adding the ultrasonicwaves, the extract amount of the antioxidant was increased. In themethod according to this example, because the extract amount of thecontent is increased, in response to a material in which the amount ofcontent to be analyzed is further minute, the content can also beaccurately analyzed in a short time.

Embodiment 8

In this example, similarly to the procedure in Example 5, a PP pellet asthe sample piece 1 including the brominated flame retardant of 100 ppmby weight was prepared. This pellet was mounted in contact with a silversubstrate as the sample table 2; then, similarly to the procedure inExample 5, after toluene as the extraction solvent 3 was dropped andinjected into the gaps between the PP pellet and the silver substrate,the sample piece was held. The sample piece was kept for 10 minutes in astate in which the toluene is maintained in the gaps between the PPpellet and the silver substrate; thereby, the brominated flame retardantwas extracted into the toluene, so that the brominated flame retardantas the deposited substance was deposited on to the silver substrate as acondensed substance. FIG. 20 is a view representing a state according tothis example, in which the content is extracted from the sample piece.As represented in FIG. 20, during the extraction operation, a silversubstrate 22, on which a PP pellet 21 is mounted, and between which andthe PP pellet 21 toluene 23 is maintained in the gaps, is placed insidea sealed container 51 in which toluene vapor is saturated. Specifically,toluene 52 that generates its vapor is contained at the bottom of thissealed container 51, and a shelf plate 53 having holes is provided onthe upper side of the toluene 52 that generates its vapor. The silversubstrate 22 is placed on the top face of this shelf plate 53, the PPpellet 21 is mounted in contact with the top face of this silversubstrate 22, and the toluene 23 is maintained in the gaps between thetop face of the silver substrate 22 and the PP pellet 21. That is,because the PP pellet 21 is stored in saturated vapor of the tolueneduring the operation in which the brominated flame retardant isextracted from the PP pellet 21, loss, due to vaporization, of thetoluene 23 as the extraction solvent can be prevented; therefore, there-dropping of the toluene 23 becomes unnecessary, and the analysisprocess becomes simple. After the extraction, the silver substrate wastaken out from the sealed container 51, the PP pellet 21 was removedfrom the silver substrate 22, and the solvent was dried with nitrogengas being blown onto the surface of the silver substrate 22, so that thebrominated flame retardant was deposited on the surface of the silversubstrate 22 as a condensed substance.

In this example, similarly to the method in Example 5, the depositedsubstance on the surface of the substrate was analyzed by thetime-of-flight secondary ion mass spectrometry method. FIG. 21 is a massspectrum of the extract, obtained by the method according to thisexample, extracted from the PP pellet including the brominated flameretardant of 100 ppm. As represented in FIG. 21, a mass spectrum peakdue to the fragment of the bromine element was observed at m/z=79.Quantitative analysis of the brominated flame retardant included in thePP pellet could be performed using the normalized (⁷⁹Br⁻/¹⁰⁷Ag⁻) peakarea ratio that is obtained from the area of the peak at m/z=79 (⁷⁹Br⁻)being normalized by the area of the peak at m/z=107 (¹⁰⁷Ag⁻) caused bythe fragment of silver in the substrate. That is, in the methodaccording to this example, not only the extraction processing time canbe considerably shortened compared to that in the conventional method,but also the re-dropping of the extraction solvent becomes unnecessary;moreover, because of the simple process, the brominated flame retardantas the content included in the PP specimen can be rapidly analyzed.

Example 9

In this example, similarly to the procedure in Example 6, an HIPS pelletincluding the brominated flame retardant of 0.1% by weight was prepared.In this example, except for a mixed solvent of toluene and methanol(toluene/methanol=1/1 by volume) in which silver perchlorate issaturated being used as the extraction solvent 3, similarly to theprocedure in Example 6, extract from the HIPS pellet was deposited as acondensed substance on the surface of the silver substrate.

In this example, similarly to the method in Example 6, the depositedsubstance on the surface of the substrate was analyzed by thetime-of-flight secondary ion mass spectrometry method. FIG. 22 is a massspectrum of the extract, obtained by the method according to thisexample, extracted from the HIPS pellet including the brominated flameretardant of 0.1%. As represented in FIG. 22, the mass spectrum peak dueto the fragments of decabromodiphenylether as brominated flame retardantand silver was observed at m/z=1068. The normalized (¹⁰⁶⁸(B+Ag)⁺/¹⁰⁷Ag⁺)peak area ratio in which the area of the peak at m/z=1068 (¹⁰⁶⁸(B+Ag)⁺)is normalized by the area of the peak at m/z=107 (¹⁰⁷Ag⁺) caused by thefragment of silver in the substrate was 0.05, which is ten times largerthan that of Example 6 in which silver perchlorate as a conductivesubstance is not added. That is, in the method according to thisexample, compared to the conventional method, not only the extractionprocessing time can be considerably shortened, but also the sensitivityfor analyzing the extract is remarkably improved; consequently, thebrominated flame retardant as the content included in the HIPS specimencan be rapidly analyzed.

INDUSTRIAL APPLICABILITY

The method of analyzing the minute quantity of the content according tothe present invention can be used for analyzing a minute quantity of acontent such as an additive included in a polymer material such asplastic, rubber, adhesives, encapsulating resin, or mold resin.Moreover, a minute quantity of a content included in a polymer materialconstituting an instrumental part such as a case, a molded product, anda printed wiring board that are manufactured using the polymer materialcan be analyzed.

1. A method of analyzing a minute quantity of content by analyzing thecontent extracted with a solvent from a material including the content,the method comprising: mounting on a sample table a sample piece of thematerial to be analyzed; dropping onto the sample table the solvent forextracting the content from the sample piece, and injecting the solventinto a gap between the sample table and the sample piece; maintaining atroom temperature the solvent injected into the gap between the sampletable and the sample piece, and, with the solvent maintained in the gapbetween the sample table and the sample piece, extracting the contentfrom the sample piece; and analyzing the content extracted from thesample piece.
 2. A method of analyzing a minute quantity of content byanalyzing the content extracted with a solvent from a polymer materialincluding the content, the method comprising: mounting, in contact withthe top face of a sample table, a sample piece of the material to beanalyzed; dropping onto the sample table the solvent for extracting thecontent from the sample piece, and injecting the solvent into a gapbetween the top face of the sample table and the sample piece mounted incontact with the top face of the sample table; maintaining at roomtemperature the solvent injected into the gap between the top face ofthe sample table and the sample piece, and, with the solvent maintainedin the gap between the top face of the sample table and the samplepiece, extracting the content from the sample piece; and analyzing thecontent extracted from the sample piece.
 3. The method of analyzing aminute quantity of content as recited in claim 2, wherein analyzing thecontent extracted from the sample piece includes a chromatographicanalysis of an analyzing solution including the content extracted fromthe sample piece.
 4. The method of analyzing a minute quantity ofcontent as recited in claim 2, wherein analyzing the content extractedfrom the sample piece includes a, after removing by vaporization of thesolvent from the solution including the content extracted from thesample piece the content onto the surface of a substrate used as thesample table, analyzing the content deposited on the surface of thesubstrate.
 5. The method of analyzing a minute quantity of content asrecited in claim 4, including analyzing the content deposited on thesurface of the substrate by time-of-flight secondary ion massspectrometry.
 6. The method of analyzing a minute quantity of content asrecited in claim 2, wherein, in extracting the content from the samplepiece, adding vibration, with the solvent maintained at roomtemperature, in the gap between the top face of the sample table and thesample piece.
 7. The method of analyzing a minute quantity of content asrecited in claim 2, wherein, in extracting the content from the samplepiece, maintaining the solvent in the gap between the top face of thesample table and the sample piece in a saturated vapor atmosphere, atroom temperature.
 8. The method of analyzing a minute quantity ofcontent as recited in claim 5, wherein the solvent, maintained in thegap between the top face of the sample table and the sample piece, forextracting the content from the sample piece additionally includes asilver composition soluble in the solvent.